JP2007086413A - Manufacturing method of plastic lens, composition for hard coat and plastic lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a plastics lens provided with an organic reflection preventing layer and having high light resistance. <P>SOLUTION: The manufacturing method of the plastics lens has a step for forming a hard coat layer by applying a first composition containing metal oxide fine particles and an organic silicon compound at a rate of 0.6 to 1.2 by weight in total on a plastics lens base material directly or via a primer layer and a step for forming the reflection preventing layer by applying a second composition containing an organic silicon compound on the hard coat layer. Thereby, the plastics lens has enhanced light resistance since the content of the metal oxide fine particles is reduced and adhesiveness can be secured. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method of manufacturing a plastic lens used for a spectacle lens.

  As a base material (fabric) for spectacle lenses, plastics are becoming the mainstream from conventional glass. A plastic lens using a plastic substrate is lighter than a glass lens using a glass substrate, has good moldability, processability and dyeability, and is also hard to break and has high safety. In addition, the plastic lens can be improved in scratch resistance by forming a hard coat layer having high hardness on the surface thereof.

  On the other hand, in order to provide a thin and lightweight spectacle lens, it is desirable to use a lens having a high refractive index, and a plastic lens substrate having a high refractive index is employed. At this time, the hard coat layer formed on the lens base material is formed of a high refractive index material or composition corresponding to the lens base material, thereby suppressing the occurrence of interference fringes.

  Patent Document 1 uses a metal oxide sol in which fine particles made of a metal oxide are colloidally dispersed in a dispersant, for example, water or another organic solvent, as a coating liquid used for the hard coat layer. In the coating liquid, it is described that an organosilicon compound and an amine compound are added within a range of about 1 to 15% with respect to the weight of the fine particles.

Patent Document 2 discloses that an antireflection film having a low refractive index containing an organic compound is provided on a plastic lens substrate by a wet method.
JP 2003-195003 A JP 2003-222703 A

  Organic anti-reflection coatings can be manufactured by applying a solution in the same manner as the hard coat layer. Furthermore, since the coefficient of thermal expansion is close to that of plastic substrates, it has excellent heat resistance, and anti-reflection of future plastic lenses. Promising as a membrane. In addition, in a plastic lens having an organic antireflection film laminated, adhesion (especially, initial adhesion) is improved, but adhesion after exposure to light for a long time (light resistance) is improved. It is requested.

  One aspect of the present invention is a method for producing a plastic lens, in which the weight ratio of the metal oxide fine particles and the organosilicon compound is 0 directly on the plastic lens substrate or with a primer layer interposed therebetween. A step of forming a hard coat layer by applying the first composition in a range of 6 to 1.2, and applying a second composition containing an organosilicon compound to the surface of the hard coat layer And a step of forming an antireflection layer.

  In the present specification, the weight ratio of the metal oxide fine particles and the organosilicon compound in the hard coat layer refers to the coating composition (first composition) for forming the hard coat layer, the lens substrate or the lens substrate, Or it is the weight ratio of metal oxide fine particles / organosilicon compound in a state where it is applied on the primer layer to complete the curing reaction. That is, the weight ratio after firing the hard coat layer. Therefore, the weight of the metal oxide fine particles is a solid weight excluding mainly volatile components such as a solvent when supplied as a sol. The weight of the organosilicon compound is the solid content weight in a state where the volatile component such as a solvent is added and the curing reaction is completed when added as a binder. The weight ratio defined above is the ratio of these solid content weights.

  According to the experiments by the present inventors, in the method for producing an organic antireflection layer on the hard coat layer, the component ratio (weight ratio after calcination) of the hard coat layer is set within the above range. In addition to heat resistance, which is a merit of the organic antireflection layer, it is possible to provide a plastic lens with improved impact resistance, scratch resistance, and light resistance.

  That is, when the weight ratio between the metal oxide fine particles and the organosilicon compound exceeds 1.2, the ratio of the metal oxide fine particles becomes too high. At this time, in the case where an inorganic antireflection layer composed of an inorganic multilayer such as silicon oxide is laminated on the hard coat layer, the higher the metal oxide ratio, the higher the adhesion between the hard coat layer and the antireflection layer, Scratch resistance and light resistance are good. In contrast, when an organic antireflection layer containing an organosilicon compound is laminated on the hard coat layer, the adhesion between the hard coat layer and the antireflection layer is improved when the ratio of the metal oxide fine particles is small. A trend is observed. That is, since the first composition for forming the hard coat layer and the second composition for forming the antireflection layer both contain an organosilicon compound, the hard coat layer and the organic antireflection layer are included. The composition is easy to cause interaction with the layer, and is a combination that easily develops adhesiveness. At this time, the heat resistance, impact resistance, and scratch resistance can be improved as the content of the metal oxide fine particles is reduced. However, if the amount is reduced too much, a refractive index with the plastic lens substrate is generated, and interference fringes are generated. Therefore, for example, it is possible to reduce the amount so that the refractive index becomes 1.6 to 1.7 according to the plastic lens base material, that is, until the weight ratio becomes about 0.6 or more. If it is in the range of 1.2, it is possible to satisfy both the durability quality such as heat resistance, impact resistance, and scratch resistance and interference fringes.

  The weight ratio between the metal oxide fine particles and the organosilicon compound, that is, “metal oxide fine particles / organosilicon compound” contributes to the refractive index of the hard coat layer formed by applying the first composition containing them. To do. Metal oxide in the first composition for forming a hard coat layer having high light resistance and suppressing generation of interference fringes on a plastic substrate having a refractive index of about 1.60 to 1.70 The weight ratio between the fine particles and the organosilicon compound is preferably 0.6 to 1.2, and more preferably 0.6 to 1.0.

  Furthermore, as a secondary effect of setting the weight ratio between the metal oxide fine particles and the organosilicon compound within the above range, the weight ratio of the organic material that functions as a binder can be increased. It becomes possible to increase the hardness of the layer, and in addition to light resistance and heat resistance, scratch resistance can also be improved.

  The metal oxide fine particles contained in the first composition for forming the hard coat layer include Si, Al, Sn, Sb, Ta, Ti, Ce, La, Fe, Zn, W, and an average particle diameter of 1 nm to 200 nm. It is desirable to include fine particles composed of one or more metal oxides selected from the element group of Zr and In and / or composite oxide fine particles composed of two or more metal oxides selected from the element group. The average particle size of the metal oxide fine particles (composite oxide fine particles) is more preferably in the range of 5 nm to 30 nm.

The organosilicon compound contained in the first composition for forming the hard coat layer is, for example, one represented by the general formula: R ³ SiX ² ₃ . R ³ represents an organic group having 3 or more carbon atoms having a polymerizable reactive group. For example, allyl group, acrylic group, methacryl group, 1-methylvinyl group, epoxy group, mercapto group, cyano group, isocyano group And polymerizable reactive groups such as amino groups. X ² represents a hydrolyzable functional group, and examples thereof include an alkoxy group such as a methoxy group, an ethoxy group, and a methoxyethoxy group, a halogen group such as a chloro group and a bromo group, or an acyloxy group. The number of hydrolyzable groups is 3, and it is necessary to be able to form a three-dimensional crosslinked structure. When the number of hydrolyzable groups is 2 or less, the abrasion resistance of the coating film is insufficient.

  The organosilicon compound contained in the first composition includes monofunctional silane, bifunctional silane, trifunctional silane, tetrafunctional silane and the like. In these compositions, the hydrolyzable group may be untreated or hydrolyzed. After the coating and forming the hard coat layer, the hydrolyzable group is preferably in a state of reacting with the -OH group of the fine particles. It is not required that all are reacted, and a sufficiently stable hard coat layer can be obtained even in a partially remaining state.

  Specific examples of the organosilicon compound contained in the first composition forming the hard coat layer are as follows. γ-glycidoxypropyltrimethoxysilane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl)- Ethyl trialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane. Two or more of these organosilicon compounds may be mixed in the first composition.

  A suitable metal oxide fine particle contained in the first composition is rutile titanium oxide. Titanium oxide can have a higher refractive index than the content. Therefore, the weight ratio of the metal oxide fine particles contained in the first composition can be reduced within the above range, and the light resistance and scratch resistance can be improved. Furthermore, rutile type titanium oxide has lower photoactivity and can improve light resistance than anatase type titanium oxide. That is, since rutile type titanium oxide has low photoactivity, decomposition due to photoactivity of the organosilicon compound contained in the hard coat layer and the antireflection layer can be suppressed.

The second composition for forming the antireflection layer preferably contains the following component (A) (hereinafter referred to as component A) and component (B) (hereinafter referred to as component B).
(A) An organosilicon compound represented by the general formula: R ¹ _p R ² _q SiX ¹ _4- qp. In the formula, R ¹ is an organic group having a polymerizable reactive group, R ² is a hydrocarbon group having 1 to 6 carbon atoms, X ¹ is a hydrolyzable group, and at least one of p and q is 1 And the other is 0 or 1.
(B) Silica-based fine particles.

R ^{1 of the} organosilicon compound of component A represents an organic group having a polymerizable reactive group. For example, a vinyl group, an allyl group, an acrylic group, a methacryl group, an epoxy group, a mercapto group, a cyano group, an amino group, and the like can be given. R ^{2 of the} organosilicon compound of component A represents a hydrocarbon group having 1 to 6 carbon atoms. Examples thereof include a methyl group, an ethyl group, a butyl group, a vinyl group, and a phenyl group. X ^{2 of the} organosilicon compound of component A represents a hydrolyzable functional group. Examples thereof include alkoxy groups such as methoxy group, ethoxy group, and methoxyethoxy group, halogen groups such as chloro group and bromo group, and acyloxy groups.

  Specific examples of the organosilicon compound of component A are as follows, for example. Tetramethoxysilane, vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, methacryloxypropyl dialkoxymethylsilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, N-β (aminoethyl) -γ- Aminopropylmethyl dialkoxysilane, tetraalkoxysilane, perfluorotrialkoxysilane, perfluorodialkoxysilane.

  A specific example of the B-component silica-based fine particles is a silica sol in which fine particles of silica having an average particle diameter of 1 nm to 100 nm are dispersed, for example, in a colloidal form in water, alcohol-based or other organic solvents. is there.

  The silica-based fine particles preferably have an internal cavity (gap). By using silica-based fine particles having internal cavities, the refractive index of the antireflection layer can be lowered, and the difference in refractive index with the hard coat layer can be increased to enhance the antireflection effect. By including a gas or solvent having a refractive index lower than that of silica in the internal cavities of the silica-based fine particles, the refractive index is lower than that of silica-based fine particles having no cavities, and a low refractive index of the coating is achieved.

  In addition to the A component and the B component, the second composition includes various resins such as a polyurethane resin, an epoxy resin, a melamine resin, a polyolefin resin, a urethane acrylate resin, and an epoxy acrylate resin, and these resins. Various monomers such as methacrylates, acrylates, epoxies, and vinyls as raw materials may be included. Examples of those having a function of reducing the refractive index include various fluorine-containing polymers and various fluorine-containing monomers. The fluorine-containing polymer is preferably a polymer obtained by polymerizing a fluorine-containing vinyl monomer, and preferably has a functional group copolymerizable with other components.

  Furthermore, the second composition can be used as a coating solution after being diluted with a solvent as required. As the solvent, solvents such as water, alcohols, esters, ketones, ethers and aromatics are used. Furthermore, the second composition may contain a small amount of a curing catalyst, a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a light stabilizer such as hindered amine / hindered phenol, a disperse dye, if necessary. -Oil-soluble dyes, fluorescent dyes, pigments, etc. can be added to improve the coating property of the coating liquid and improve the film performance after curing.

  Further, in the above manufacturing method, the step of forming the hard coat layer and the step of forming the antireflection layer are respectively a step of baking the hard coat layer (which may include a primer layer) and a step of baking the antireflection layer. The process of carrying out is included. In each step, each layer is independently fired at about 80 to 140 ° C. Characteristics such as durability, scratch resistance, and heat resistance may be affected by the firing temperature conditions. For example, the characteristics may be improved by firing the primer layer and the hard coat layer in a low temperature range of about 80 to 100 ° C. and firing the antireflection layer in a high temperature range of about 120 to 140 ° C. This tendency is remarkable in the case where the weight ratio of the metal oxide fine particles to the organosilicon compound in the hard coat layer is in the range of 0.6 to 1.2, that is, in the configuration in which the organosilicon compound is large relative to the metal oxide fine particles. Tend to be. By firing the primer layer and the hard coat layer in a low temperature region to control the curing reaction of those layers, and then firing the antireflection layer in a high temperature region, the lower layer (primer layer and hard coat layer) and the upper layer ( It is possible to further improve the adhesion of both of the antireflection layers.

  Another aspect of the present invention is a first composition used for forming a hard coat layer in the method for producing a plastic lens, wherein the metal oxide fine particles and the organosilicon compound are combined with each other. Is included in a range of 0.6 to 1.2.

  Furthermore, another embodiment of the present invention is a plastic lens obtained by the above-described method for producing a plastic lens. This plastic lens comprises a plastic lens base material, and metal oxide fine particles and an organosilicon compound, which are formed directly or sandwiching a primer layer, on a weight ratio of 0.6 to 1.2. And a hard coating layer included in the range, and an antireflection layer containing an organosilicon compound formed on the hard coating layer. This antireflection layer preferably contains the A component and the B component. As described above, this plastic lens is excellent in light resistance and scratch resistance in addition to heat resistance, and is suitable as a plastic spectacle lens.

  In the following, some processes for manufacturing a plastic lens for spectacles will be described.

Example 1
In Example 1, a primer layer, a hard coat layer and an antireflection layer were added to a thiourethane plastic lens substrate (manufactured by Seiko Epson Corporation, trade name “Seiko Super Sovereign Fabric (SSV)”, refractive index 1.67). In order to produce a plastic lens. First, the lens substrate was immersed in an alkali treatment solution (2.0 N potassium hydroxide aqueous solution kept at 50 ° C.) for 5 minutes, and then washed with pure water. Furthermore, it was neutralized by immersion for 1 minute in 0.5 N sulfuric acid kept at 25 ° C., washed with pure water, dried and allowed to cool.

(Step of forming a primer layer)
The coating liquid (primer composition) P for applying the primer layer was prepared as follows. First, 3700 parts by weight of methyl alcohol, 250 parts by weight of water, and 1000 parts by weight of propylene glycol monomethyl ether were put into a stainless steel container and sufficiently stirred. Thereafter, composite fine particle sol mainly composed of titanium oxide, zirconium oxide, and silicon oxide (anatase type crystal structure, methanol dispersion, manufactured by Catalytic Chemical Industry Co., Ltd., trade name “Optlake 1120Z U-7 · G”) 2800 parts by weight were added and mixed with stirring. Next, 2200 parts by weight of a polyester resin was added and mixed with stirring. Thereafter, 2 parts by weight of a silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “L-7604”) was further added. And after continuing stirring all day and night, it filtered with a 2 micrometer filter. And the primer composition P was obtained in order to form a primer layer by application | coating.

  This primer composition P was applied to the lens substrate subjected to the above treatment by dipping. The pulling speed is 30 cm / min. Then, it baked at 80 degreeC for 20 minutes, and formed the primer layer on the surface of a lens base material.

(Step of forming a hard coat layer)
A coating liquid (hard coat composition, first composition) HC for forming a hard coat layer by coating was prepared as follows. First, 1000 parts by weight of butyl cellosolve and 1200 parts by weight of γ-glycidoxypropyltrimethoxysilane as an organosilicon compound were added to a stainless steel container and sufficiently stirred. Thereafter, 300 parts by weight of 0.1 mol / liter hydrochloric acid was added and stirring was continued for one day to obtain a silane hydrolyzate. To this silane hydrolyzate, 30 parts by weight of a silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “L-7001”) was added and stirred for 1 hour. Thereafter, as a metal oxide fine particle, a composite fine particle sol mainly composed of titanium oxide, tin oxide, and silicon oxide (rutile type crystal structure, methanol dispersion, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “Optlake 1120Z 8RU-25, A17 ") 7300 parts by weight were added. And these were stirred and mixed for 2 hours. Next, 250 parts by weight of an epoxy resin (manufactured by Nagase Kasei Co., Ltd., trade name “Denacol EX-313”) was added and stirred for 2 hours. Then, 20 parts by weight of iron (III) acetylacetonate and 10 parts by weight of 4,4′-thiobis (6-tert-butyl-meta-cresol) are added, stirred for 3 hours, and filtered through a 2 μm filter. went. And the hard-coat composition HC for forming a hard-coat layer by application | coating was obtained.

  The composite fine particle sol mainly composed of titanium oxide, tin oxide, and silicon oxide and γ-glycidoxypropyltrimethoxysilane (organosilicon compound) contained in the hard coat composition HC are sintered, When the total weight of the metal oxide fine particles and the organosilicon compound is 100, the metal oxide fine particles are 52 and the organosilicon compound is 48. That is, the weight ratio (metal oxide fine particles / organosilicon compound) R is adjusted to 1.08.

  This hard coat composition HC was applied to a lens substrate with a primer layer by dipping. The pulling speed is 30 cm / min. Then, it baked at 80 degreeC for 30 minutes, and heated in the oven set to 125 degreeC for 3 hours. At this stage, a plastic lens having a primer layer and a hard coat layer was obtained. The formed primer layer had a thickness of 0.5 μm and the hard coat layer had a thickness of 2.5 μm.

(Step of forming an antireflection layer)
A coating liquid (antireflection composition, second composition) AR for forming an organic antireflection layer by coating was prepared as follows. First, 208 parts by weight of tetramethoxysilane as an organosilicon compound is put into a stainless steel container, 356 parts by weight of methanol is added, 18 parts by weight of water, and 18 parts of 0.01N hydrochloric acid aqueous solution are added. And mixed well to obtain a mixed solution. This mixed solution was stirred for 2 hours in a thermostatic bath at a temperature of 25 ° C. to obtain a silane hydrolyzate. In this silane hydrolyzate, hollow silica-isopropanol dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content concentration 20%, average primary particle diameter 35 nm, outer shell thickness 8 nm) was added as silica fine particles. This silica fine particle was mix | blended so that it might become a weight ratio 60/40 with respect to a silane hydrolyzate. Subsequently, 1 part by weight of a silicone-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “L-7001”) was mixed. Then, it diluted with propylene glycol monomethyl ether so that the total solid content might be 2%, and obtained composition AR for antireflection.

  This antireflection composition AR was applied by dipping to a lens substrate on which a primer layer and a hard coat layer were formed. The pulling speed is 5 cm / min. Prior to coating, the surface of the hard coat layer was treated with plasma (atmospheric plasma). After coating, it was then fired at 80 ° C. for 30 minutes, and further heated in an oven set at 100 ° C. for 2 hours. At this stage, a plastic lens in which a primer layer, a hard coat layer, and an organic antireflection layer are sequentially formed on the lens substrate is obtained, and the thickness of the formed antireflection layer is 100 nm. there were.

  The plastic lens manufactured according to Example 1 was subjected to the tests described below to evaluate each characteristic. The results are summarized in FIG. The evaluation method and the results will be described together below. The same applies to the following examples and comparative examples.

(Example 2)
In Example 2, as in Example 1, using SSV with a refractive index of 1.67 as a lens substrate, a step of forming a primer layer, a step of forming a hard coat layer, and a step of forming an antireflection layer To produce a plastic lens.

  However, in the step of forming the hard coat layer, the metal oxide fine particles contained in the hard coat composition HC (as described above, trade name “OPTRAIQUE 1120Z 8RU-25, A17” manufactured by Catalyst Chemical Industry Co., Ltd.) and When the total weight of the metal oxide fine particles and the organosilicon compound is defined as 100 after the amount of preparation of the organosilicon compound with γ-glycidoxypropyltrimethoxysilane is baked, the metal oxide fine particles are 46 In contrast, the organosilicon compound was 54, and the weight ratio R thereof was 0.85.

(Example 3)
In Example 3, as in Example 1, the step of forming a primer layer, the step of forming a hard coat layer, and the step of forming an antireflection layer were performed using SSV having a refractive index of 1.67 as a lens base material. A plastic lens was manufactured.

  However, in the step of forming the hard coat layer, the metal oxide fine particles contained in the hard coat composition HC (as described above, trade name “OPTRAIQUE 1120Z 8RU-25, A17” manufactured by Catalyst Chemical Industry Co., Ltd.) and When the total weight of the metal oxide fine particles and the organosilicon compound is 100 after the amount of the organosilicon compound and γ-glycidoxypropyltrimethoxysilane being baked, the metal oxide fine particles are 40 In contrast, the organosilicon compound was 60, and the weight ratio R thereof was 0.67.

Example 4
In Example 4, as in Example 1, a thiourethane-based plastic substrate having a refractive index of 1.60 (manufactured by Seiko Epson Corporation, trade name “Seiko Super Lucent Fabric (SLU)”) is used as a lens substrate. A plastic lens was manufactured by performing a step of forming a primer layer, a step of forming a hard coat layer, and a step of forming an antireflection layer.

  However, in the step of forming the hard coat layer, the metal oxide fine particles contained in the hard coat composition HC (as described above, trade name “OPTRAIQUE 1120Z 8RU-25, A17” manufactured by Catalyst Chemical Industry Co., Ltd.) and When the total weight of the metal oxide fine particles and the organosilicon compound is 100 after the amount of the organosilicon compound and γ-glycidoxypropyltrimethoxysilane being baked, the metal oxide fine particles are 40 In contrast, the organosilicon compound was 60, and the weight ratio R thereof was 0.67.

(Example 5)
In Example 5, as in Example 1, a thiourethane plastic substrate having a refractive index of 1.70 (manufactured by Seiko Epson Corporation, trade name “Seiko Lapidary Fabric (LPD)”) was used as a lens substrate. A plastic lens was manufactured by performing a step of forming a primer layer, a step of forming a hard coat layer, and a step of forming an antireflection layer.

  However, in the step of forming the hard coat layer, the metal oxide fine particles contained in the hard coat composition HC (as described above, trade name “OPTRAIQUE 1120Z 8RU-25, A17” manufactured by Catalyst Chemical Industry Co., Ltd.) and When the total weight of the metal oxide fine particles and the organosilicon compound is 100 after the amount of the organosilicon compound and γ-glycidoxypropyltrimethoxysilane being baked, the metal oxide fine particles are 54 In contrast, the organosilicon compound was 46, and the weight ratio R thereof was 1.17.

(Comparative Example 1)
In Comparative Example 1, as in Example 1, the step of forming a primer layer, the step of forming a hard coat layer, and the step of forming an antireflection layer were performed using SSV having a refractive index of 1.67 as a lens base material. A plastic lens was manufactured.

  However, in the step of forming the hard coat layer, the metal oxide fine particles contained in the hard coat composition HC (as described above, trade name “OPTRAIQUE 1120Z 8RU-25, A17” manufactured by Catalyst Chemical Industry Co., Ltd.) and When the total weight of the metal oxide fine particles and the organosilicon compound is 100 after the amount of the organosilicon compound and γ-glycidoxypropyltrimethoxysilane being baked, the metal oxide fine particles are 60 In contrast, the organosilicon compound was 40, and the weight ratio R thereof was 1.50.

(Comparative Example 2)
In Comparative Example 2, as in Example 1, the step of forming a primer layer, the step of forming a hard coat layer, and the step of forming an antireflection layer were performed using SSV having a refractive index of 1.67 as a lens base material. A plastic lens was manufactured.

  However, in the step of forming the hard coat layer, the metal oxide fine particles contained in the hard coat composition HC (as described above, trade name “OPTRAIQUE 1120Z 8RU-25, A17” manufactured by Catalyst Chemical Industry Co., Ltd.) and When the total weight of the metal oxide fine particles and the organosilicon compound is defined as 100 after the amount of preparation of the organosilicon compound with γ-glycidoxypropyltrimethoxysilane is baked, the metal oxide fine particles are 30 In contrast, the organosilicon compound was 70, and the weight ratio R thereof was 0.43.

(Evaluation methods)
The physical property of the plastic lens (sample lens) manufactured by the above Examples 1-5 and Comparative Examples 1-2 was evaluated by the evaluation method shown below. The results are summarized in FIG. The evaluation items (physical properties) are nine items of interference fringes, reflectance, scratch resistance, initial adhesion, moisture resistance, warm water resistance, light resistance, heat resistance, and impact resistance.

  In the evaluation of interference fringes, the sample lens was held directly under a three-wavelength fluorescent lamp, and the occurrence of interference fringes on the lens surface was confirmed visually. “◯” indicates that almost no interference fringes are generated, and “x” indicates that the interference fringes are clearly recognized.

  In the evaluation of the reflectance (antireflection effect), the surface reflectance of the sample lens is measured with a spectrophotometer (manufactured by Hitachi, Ltd., model number “U-3500”), and the visibility is corrected according to the measured visibility curve. It was converted to the reflectance.

  In the evaluation of scratch resistance, steel wool (# 0000) was applied to the surface of the sample lens with a load of 1 kg, and after rubbing 10 times in a distance of 3 to 4 cm, the state of scratches that entered the surface of the sample lens was visually observed. confirmed. “◯” indicates that no scratches are visible, and “X” indicates that the scratches are clearly visible.

  In the evaluation of initial adhesion, the surface of the sample lens was cross-cut into a grid pattern at intervals of about 1 mm. An adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Cerotape (registered trademark)”) was strongly attached to the cross-cut portion, and then the adhesive tape was rapidly peeled off. Then, the film peeling state of the grid was confirmed visually. “◯” indicates that there is no film peeling, and “×” indicates that there is film peeling.

  In the evaluation of moisture resistance, the sample lens was left in a constant temperature and humidity furnace (40 ° C., 90 RH%) for 10 days, and then the sample lens was taken out from the constant temperature and humidity furnace and left at room temperature for 3 hours. An adhesion test was performed. The adhesion test was performed by the same method and the same evaluation criteria as the above initial adhesion.

  In the evaluation of hot water resistance, the sample lens was immersed in warm water at 80 ° C. for 2 hours, and then the sample lens was taken out from the warm water and cooled with water, and then an adhesion test was performed. This adhesion test was also performed by the same method and the same evaluation criteria as the above initial adhesion.

  In the light resistance evaluation, the sample lens was irradiated with a xenon long life weather meter (manufactured by Suga Test Instruments Co., Ltd.) for 200 hours, and the sample lens was taken out of the xenon long life weather meter and cooled with water, and then an adhesion test. Went. This adhesion test was also performed by the same method and the same evaluation criteria as the above initial adhesion.

  In the evaluation of heat resistance, the sample lens was glazed according to the shape of the spectacle frame, then fitted into the spectacle frame, completely tightened with screws, and placed in a constant temperature bath at 60 ° C. for 30 minutes. Thereafter, the sample lens was taken out, allowed to cool at room temperature for 1 hour, and then evaluated for occurrence of cracks. In the case where no cracks were generated, it was added to a constant temperature bath at 65 ° C. for 30 minutes, and then the presence or absence of cracks was evaluated. Thereafter, the temperature was increased by 5 ° C., and the temperature was further increased for 30 minutes, and the temperature at which cracks occurred was defined as the heat resistant limit temperature.

  For impact resistance, in a test in which a 16.3 g hard sphere was dropped vertically onto the sample lens surface, the drop height was increased from 127 cm to 10 cm intervals, and the drop height at the time of breaking or penetrating was measured.

  In the sample lenses manufactured in Examples 1 to 5, no interference fringes are visible, and the reflectance (antireflection effect) is as low as 0.5, which is good, scratch resistance, initial adhesion, and moisture resistance. Moreover, warm water resistance and light resistance are also good. Furthermore, the heat resistance is as good as 125 ° C. or more, and the impact resistance is excellent as 200 cm or more.

  On the other hand, in the sample of Comparative Example 1 in which the content of the metal oxide fine particles is too high, some of the physical properties are inferior to those of the other Examples. For example, the sample of Comparative Example 1 has low scratch resistance and light resistance compared to other Examples, and the heat resistance is not so high as 100 ° C.

  In the sample of Comparative Example 2 in which the content of metal oxide fine particles is too small, the refractive index of the hard coat layer is low, so that interference fringes are visible and the optical properties are inferior.

  Therefore, in a plastic lens in which an organic antireflection layer is stacked on a hard coat layer, the amount of metal oxide fine particles contained in the hard coat layer is high, and the adhesion, particularly after the exposure test, is reduced. It can be seen that the mechanical properties are affected. In plastic lenses with organic antireflection layers, metal oxide fine particles are used to ensure the adhesion of these layers, such as plastic lenses with an inorganic antireflection layer formed on a hard coat layer. Therefore, the amount of metal oxide fine particles having photoactivity can be reduced to the extent that the optical properties of the plastic lens can be ensured. For this reason, in the plastic lens manufactured by Examples 1-5, ie, the plastic lens provided with the hard-coat layer which contains metal oxide microparticles | fine-particles and an organosilicon compound in the range of weight ratio R0.6-1.2, light resistance And a plastic lens with good optical properties can be obtained.

  Thus, in a plastic lens in which an organic antireflection layer is provided on the hard coat layer, the adhesiveness can be ensured by reducing the content of metal oxide fine particles, so that the light resistance can be improved. Furthermore, the plastic lens provided with the hard coat layer containing the metal oxide fine particles and the organosilicon compound in the range of the weight ratio of R0.6 to 1.2 has high heat resistance and high scratch resistance. .

The figure which shows the lens structure and evaluation result which concern on an Example and a comparative example.

Claims (5)

A first composition comprising metal oxide fine particles and an organosilicon compound in a weight ratio of 0.6 to 1.2 directly on a plastic lens substrate or sandwiching a primer layer Forming a hard coat layer by applying
And a step of forming an antireflection layer by applying a second composition containing an organosilicon compound to the surface of the hard coat layer.   2. The method for producing a plastic lens according to claim 1, wherein the metal oxide fine particles contained in the first composition contain rutile titanium oxide. 3. The method for producing a plastic lens according to claim 1, wherein the second composition includes the following components (A) and (B):
(A) the general ^{_{formula: R 1 p R 2 q SiX}} 1 4-q-p organic silicon compound represented by (wherein, ^{R 1} represents an organic group having a polymerizable reactive group, ^{R 2} is 1 to the number of carbon atoms 6 hydrocarbon group, X ¹ is a hydrolyzable group, and at least one of p and q is 1 and the other is 0 or 1.)
(B) Silica-based fine particles   A composition for forming a hard coat layer on a plastic lens substrate by coating directly on the plastic lens substrate or sandwiching a primer layer, the metal oxide fine particles and the organic silicon And a compound having a weight ratio of 0.6 to 1.2.   The plastic lens obtained by the manufacturing method of the plastic lens in any one of Claim 1 thru | or 3.

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